Use of o,o-di-(c1-c2 alkyl)s-(1-(c2-c20 acyl)hydantoin-3-yl)methyl phosphorothioates as insecticides

ABSTRACT

DISCLOSED IS AN INSECTICIDAL COMPOSITION COMPRISING COMPOUNDS OF THE FORMULA:   1-(R2-CO-),3-((R&#39;&#39;-O-)2-P(=Y)-S-CH2-),5-R3,5-R4-   IMIDAZOLIDINE-2,4-DIONE   IN WHICH R&#39;&#39; IS CH3 OR CH2H5, R2 IS C1-C19 ALKYL, R3 AND R4 ARE H OR CH3, AND Y IS O OR S AND A PROCESS FOR KILLING INSECTS.

United States Patent USE OF O,O-DI-(C -C ALKYL)S-[1-(C -C ACYL)HYDANTOIN-3-YL1METHYL PHOSPHOROTHIO- ATES AS INSECTICIDES Albert H.Haubein, Newark, Del., assignor to Hercules Incorporated, Wilmington,Del.

No Drawing. Application Oct. 29, 1970, Ser. No. 85,298,

now Patent No. 3,687,966, which is a continuation-inpart of abandonedapplication Ser. No. 694,861, Jan. 2, 1968. Divided and this applicationJan. 10, 1972, Ser. No. 216,858

Int. Cl. A01n 9/36 US. Cl. 424-200 3 Claims ABSTRACT OF THE DISCLOSUREDisclosed is an insecticidal composition comprising compounds of theformula:

in which R is CH, or C H R is C -C alkyl, R and R are H or CH and Y is Oor S and a process for killing insects.

The application is a division of the application, Ser. No. 85,298, onwhich US. Pat. 3,687,966 was granted, which was filed Oct. 29, 1970, asa continuation-in-part of the application, Ser. No. 694,861, filed Jan.2, 1968, now abandoned.

This invention is in the chemical arts. It relates to that part oforganic chemistry relating to organophosphorus compounds and toorganophosphorus insecticides.

In summary, this invention provides a new group of organophosphoruscompounds represented by the formula:

in which each R is selected from the group consisting of CH, and C H Ris C -C alkyl, R and R are selected from the 'group consisting of H orCH and Y is selected from the group consisting of O and S. In theformula, C -C alkyl covers both straight and branched chain alkyls with1-19 carbon atoms. Representative compounds of the group are listed bytheir structural formulas in the following Table.

The compounds of this invention in general at 2025 C. are yellow tobrown liquids. They are insoluble in water, but soluble in solvents likeacetone and in solvents like benzene.

Patented June 11, 1974 The compounds of this invention are highly toxicto insects. This is exemplified by the typical insect mortality datapresented in the following Table for the representative compounds listedtherein. The Table also contains the physical state at 20-25 C. of eachof the end products obtained when the compounds are made according tothe procedures in Examples 1 and 2.

Each of the compounds of this invention is made by the followingreaction procedure. A hydantoin of the formula: v

is reacted with the anhydride of a C -C alkanoic acid to form thecorresponding l-acylhydantion of the formula:

Tins compound is reacted with formaldehyde to form the corresponding3-hydroxymethyl-l-acylhydantoin:

which is reacted with P01 PBr or the like to form the corresponding3-chloromethyl or 3-bromomethyl compound:

I ll R 0 wherein X is Cl or Br. The 3-chloromethyl or 3-bromomethylcompound is reacted with a thiophosphate of the in which M is H, NH, ormetallic anion, to form the compound of this invention. In the foregoingformulas R R R and R have the same meanings as in the generic formulafor the compounds of this invention.

220% by weight of the composition, while the granular carrier materialis generally about 80-98% by weight of the composition.

The incorporated type of granular composition is made by admixing theinsecticidal material with an inert finely divided solid such as, forexample, clay, carbon, plaster of Paris and the like, and made into amud with water or other inert evaporable liquid. The mud is then driedto a solid sheet or cake, broken up or comminuted, and screened to thedesired particle size (generally 15-60 mesh, preferably about 30 mesh,U.S. screen size). In other embodiments, the mud is put into a granularpan and granules are formed therein with subsequent removal of the wateror solvent. In still another procedure, the mud is extruded through adie into rods which are cut into small pieces. In the incorporated typeof granular composition, the insecticidal material generally is about2-50'% by weight of the composition, and the solid carrier material isabout 50-98% by weight of the composition.

In all granular embodiments of the composition of this invention,various additives in minor concentrations relative to the carriermaterial also can be present.

In other embodiments of the solid composition of this invention, thecarrier is usually a dispersible inert solid. A typical dispersiblesolid of this type is clay. Other suitable solids (dispersible solid)include talc, attapulgite, pyrophylite, diatomaceous earth, kaolin,aluminum magnesium silicate, montmorillonite, fullers earth, sawdust andthe like. The solid dispersible composition can be air dispersible, inwhich case it is usually referred to as a dust. Generally, when it isintended that the composition be water dispersible, the compositionpreferably contains emulsifying material (one or more surfactants) at aconcentration sufficient to enable a suspension of the desired degree ofstability to be formed when the composition is admixed with a suitablequantity of water. The composition in such case is usually referred toas a wettable powder. A typical dispersible solid composition of thisinvention generally comprises about 10-50'% by weight of insecticidalmaterial, about 50-90% by weight of solid carrier material and, whenemulsifying material is present, about 110% by weight of emulsifyingmaterial.

Other specific embodiments of the insecticidal composition of thisinvention comprise homogeneousliquid solutions of insecticidal materialin inert, preferably volatile, usually water immiscible solvents for theinsecticidal material. Examples of suitable solvents include isophorone,cyclohexanone, methyl isobutyl ketone, xylene, and the like. Such asolution, which can be regarded as a concent-rate, typically comprisesabout 10-50% by weight of insecticidal material and about 50-9 by weightof solvent. The solution can be applied as is, or diluted with moresolvent, or dispersed in water, or water dispersed in it. Preferably,when it is intended that the solution be dispersed in water or waterdispersed in it, the mixture of solution and water also comprisesemulsifying material at a concentration sufiicient to enable adispersion (an aqueous emulsion) of the desired degree of stability tobe formed when the solution or concentrate is mixed with water. Atypical emulsifying material concentration is about 1-10% by weight ofthe concentrate. The water concentration generally is such that theinsecticidal material concentration preferably is about 05-10% by weightof the total composition.

Examples of the surfactants employed in both the liquid and solidcompositions of this invention comprise the well-known surface activeagents of the anionic, cationic and non-ionic types and include alkalimetal (sodium or potassium) oleates and similar soaps, amine salts oflong chain fatty acids (oleates), sulfonates, animal and vegetable oils(fish oils and castor oil), sulfonated acyclic hydrocarbons, sodiumsalts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates,sodium lauryl sulfonate, disodium monolauryl phosphate, sorbitollaurate, pentaerythritol monostearate, glycerol monostearate,polyoxyethylene, ethylene oxide condensates of stearic acid, stearylalcohol, stearyl amine, rosin amines, dehydroa'bietyl amine and thelike, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridiniumbromide, stearyl trimethylammonium bromide, and cetyldimethylbenzylammonium chloride. Still other examples are listed inDetergents and Emulsifiers-1968 Annual by John W. Mc- Cutcheon.

In addition to the insecticidal material and application aid material,some specific embodiments of the insecticidal composition of thisinvention comprise one or more other components, examples of whichinclude insect attractants, herbicides, fungicides, plant nutrients, andthe like.

The insecticidal composition of this invention is used by applying it byconventional ways and means to the habitats of the insects to becontrolled. When it is desired to take advantage of the systemictoxicity of systemically active insecticidal material, the compositionis applied as by spraying to the seeds of plants on which thesystemically affected insects feed prior to planting, by laying ordrilling the composition in granular form next to or with the seedsbeing planted, or spraying or dusting the leaves of the growing plantsin the early stages of their growth.

The rate of application of the composition of this invention is such asto provide an effective concentration of the insecticidal material inthe insect habitat to which the composition is applied. This varies withthe insect or insects to be controlled, and the composition of theinsecticidal material.

The best mode now contemplated of carrying out this invention isillustrated by the following working examples of various aspects of thisinvention, including specific embodiments. This invention is not limitedto these specific embodiments. In these examples all percentages are byweight unless otherwise indicated, all parts by weight are indicated byw., all parts by volume are indicated by v., and each part by weight(w.) bears the same relationship to etch part by volume (v.) as thekilogram does to the liter.

EXAMPLE 1 This example illustrates how to make Compound No. 15 of theTable, which is 0,0-dimethyl S-(l-hexanoylhydantoin-3-yl)-methylphosphorodithioate.

A mixture of hexanoic anhydride (102 w.), hydantoin (34 w.) andconcentrated H SO (0.05 w.) is heated at C. for 12 hours. On cooling,crystals typically form. Benzene (100 -v.) is added and the mixturewarmed until the crystals go into solution. Hexane is aded until thesolution becomes cloudy, and the reaction mixture cooled to 20-25 C. Theresulting crystals (44.6 w.) are collected and recrystallized frombenzene-hexane. They typically are white and having a melting point of75-77 C. They consist essentially of l-hexanoylhydantoin.

To the l-hexanoylhydantoin product (20 w.) in n-butyl acetate v.) areadded paraformaldehyde (3 w.) and pyridine (0.13 w.). The resultingsolution is refluxed for 5 hours, cooled, and hexane is added until thesolution becomes cloudy. After standing a short time, crystals form.These crystals are removed by filtration from the reaction mixture, andresidual solvent is removed by evaporation. The product (13.2 w.)typically has a melting point of 96-98 C. It consists essentially ofl-hexanoyl- 3-hydroxymethyl hydantoin. v

To 1-hexanoyl-3-hydroxymethyl hydantoin (49.9 w.) made as above andsuspended in methylene chloride (75 v.) and cooled to minus 15-minus'25C., potassium tribromide (18.5 w.) is added over a period of 30 minutes.The resulting mixture is stirred one hour at 20-25 C. and refluxed forthree hours. The reaction mass is cooled to 20-25 C. and washed threetimes with brine. The solvent is removed at 18 millimeters of mercurypressure to a pot temperature of 80 C. The residue is recrystallizedfrom carbon tetrachloride-hexane to give a typically white crystallineproduct (35.6 w.) having a melting point of 45- 46 C. This productconsists essentially of 3-bromomethyl-l-hexanoylhydantoin.

To the 3-bromomethyl-l-hexanoylhydantoin product (29 W.) in acetonitrile(100 v.) is added with stirring ammonium dimethyl phosphorodithioate(17.5 w.). The reaction is slightly exothermic, the temperature of thereaction mixture increasing from 25 to 32 C. without external cooling.Ammonium chloride precipitates as the reaction proceeds. After 16 hoursat-2025 C. the stirred suspension is heated to 55 C. for 2% hours,cooled, poured into water, and extracted with diethyl ether. The etherextract is washed with water, dried over anhydrous sodium sulfate, andthe solvent removed under a vacuum of 18 millimeters mercury pressure toa pot temperature of 80 C. The residue is then topped at 80 C. and 0.5millimeter of mercury pressure to leave a typically yellow liquid (31.2w.). It is recrystallized from benzene-petroleum ether to give thedesired product which typically is in the form of white crystals, themelting point of which is 6567 C. This product consists essentially of0,0- dimethyl S-( l-hexanoylhydantoin-Ii-yl) methyl phosphorodithioate.

In similar manner the other dithioate compounds of this invention aremade from C -C alkanoic anhydrides, a hydantoin selected from the groupconsisting of hydantoin, S-methyl-hydantoin and 5,5-dimethyl hydantoin,and an ammonium phosphorodithioate selected from the group consisting ofammonium 0,0-dimethyl phosphorodithioate, ammonium 0,0-diethylphosphorodithioate and ammonium O-methyl O-ethyl phosphorodithioate.

EXAMPLE 2 This example illustrates how to make Compound No. 16 of theTable, which is 0,0-dimethyl S-(hexanoylhydantoin-3-yl) methylphosphorothioate.

To a 3-bromomethyl-l-hexanoylhydantoin product (78 w.) made according toExample 1 and in acetonitrile (165 v.) is added with stirring ammoniumdimethyl phosphorothioate (42.9 w.). The procedure described in Example1 for reacting the 3-bromomethyl compound with the ammonium compound andfor obtaining the desired end product is followed. The product thusobtained is typically a pale yellow liquid consisting essentially of0,0-dimethyl S-(1-hexanoylhydantoin-3-yl) methyl phosphorothioate.

In similar fashion the monothioate compounds of this invention are madefrom C C alkanoic anhydrides, a hydantoin selected from the groupconsisting of hydantoin, S-methylhydantoin and 5,5-dimethylhydantoin,and an ammonium phosphorothioate selected from the group consisting ofammonium 0,0-dimethyl phosphorothioate, ammonium 0,0-diethylphosphorothioate, and ammonium O-methyl O-ethyl phosphorothioate.

EXAMPLE 3 This example illustrates a Water emulsifiable concentrateformulation in which the compounds of this invention can beincorporated.

The formulation is:

Components: Concentration Toxic material l w. Polyoxyethylene (20)sorbitan monolaurate 1 v. Toluene or benzene l v.

The toxic material consists essentially of one or more compounds of thisinvention. The polyoxyethylene (20) sorbitan monolaurate is anemulsifier in which the oxyethylene content averages about 20 molepercent.

The concentrate of this formulation is made by admixing the componentsat 20-25 C.

The concentrate is used, for example, by admixing it with water untilthe toxic material in the resulting emulsion is at the desiredconcentration, and the emulsion thus formed is applied to the habitat ofthe insect to be controlled. v

The test data in the Table were obtained by incorporating each compoundlisted in the Table into an emulsifiable concentrate of the foregoingformulation, admixing portions of the concentrate with water to giveemulsions with the toxic material at the concentrations indicated in theTable, and then applying these emulsions according to the followingstandard, routinely carried out test procedures,

House fly--25 unsexed 3 to 4 day old house flies immobilized by C0 areplaced in a 14 mesh screen wire cage (5.5 mesh/cm., wire size 0.0355 cm.diameter, mesh opening 1.45 mm.), cylindrical in shape, with a 12.7 cm.diameter and a 5 cm. depth, and sprayed with a con trolled mist-likedispersion of emulsion in an enclosed tower for 10 seconds. Afterspraying, the cages of flies are placed in a holding room at 78 F. and50% relative humidity, and a 5% aqueous sugar solution is placed in thecage for feeding purposes. The number of flies killed is determined 24hours later.

Mexican bean beetleA freshly cut 7 cm. leaf of a lima bean plant issupported by its stem placed in a cotton-stoppered 3.5 ml. water-filledvial, and the leaf is sprayed on the upper surface with emulsion, andallowed to dry. The leaf in its vial is placed in a plastic sandwich box11 cm. x 13 cm. x 4 cm. with 10 Mexican bean beetle larvae (2nd to 3rdinstar) and kept at 78 F. and 50% relative humidity for 48 hours. Thedead larvae are then counted.

Pea aphidA small pea plant is placed in a cylindrical wire-screen cage,10 adult pea aphids are sprayed with emulsion, and placed on the plants.The cage is stored for 24 hours at 60-65 F. and 50% relative humidity.The percent mortality is then determined.

Two-spoted miteLima bean seedlings 5 to 6' days old are infested with 50phosphate resistant two-spotted mites at various growth stages, and theemulsion is sprayed on both sides of the leaves of the infested plantsto run oif. The seedling stems are placed in fresh water, and theinfested plants kept at 78 F. and 50% relative humidity for 6 days. Thenthe mortality is determined.

Plum curculio-Small green apples are sprayed with emulsion, dried andplaced plastic cups infested with 10 adult curculios. After storage ofthe cups for 6 days at 78 F. and 50% relative humidity, the number ofdead curculios is determined.

Corn root wormIna 15 ml. plastic cup are placed a freshly sproutedkernel of corn, and on top of the kernel 10 cc. of damp sand so that thesprout is completely covered. This cup is then placed in a spray chamberin which a spray of the emulsion is directed into the cup Two-spottedmite and pea aphid, systemic-Potted lima bean seedlings (5 to 6 daysold) which have been grown under the temperature and relative humidityconditions of the test are placed in culture tubes containing emulsion.After 24 hours, 50100 two-spotted mites are placed on the leaves of onesuch seedling, and 10 adult aphids on another. These culture tubes arethen stored at 78F. and 50% relative humidity. The mortality of aphidsis determined after 2 days, and the mortality ofmites is ascertainedafter 6 days.

Southern armyworm A freshly cut 7 cm. leaf ofal lima bean plant issupported by its stem placed in a cotton-stoppered 35ml. water-filledvial, and the leaf is sprayed on the upper surface with emulsion andthen allowed to dry. The leaf its vial is placed in a plastic sandwichbox 11 cm. x 4 cm. with 10 armyworm larvae (3rd to 4th instar), and heldat 78 F. and 50% relative humidity for 48 hours, and the mortalitydetermined at the end of this time.

Southern armyworm-Systemic-This test is carried out in the same manneras the pea aphid systemic test, except ten 2nd-3rd instar larvae of thesouthern armyworm are used.

Southern armwormsystemic-seed treatment-In this test soil is placed inan aluminum dish about 5 inches long. Five lima bean seeds are plantedin a furrow in the soil. The seeds in the furrow are sprayed withemulsion at a rate equivalent to 5 pounds per acre of the toxic materialbeing tested. The seeds are covered with soil and the dish is placed ina greenhouse under temperature and humidity conditions favorable forrapid germination and sprouting. A week later, the resulting bean leavesare infested with ten 2nd-3rd instar larvae of the southern armworm.After storage for 48 hours under the same temperature and humidityconditions, mortality counts are taken.

Thus, this invention provides valuable compounds and compositions forinsect control. A surprising aspect of the compounds of this inventionis that as the number of carbon atoms in the C -C acyl group at the 1position of the hydantoinyl moiety increases in the range of 2 through20, the insecticidal activity of the molecule remains high. In otherinsecticidal organo-phosphorus molecules, the insecticidal activitydecreases as molecular weight increases.

A feature of advantage of the compounds of this invention is that theyin general are substantially more effective as systemic toxicants forthe southern armyworm than comparable compounds in the prior art.

Still another feature of advantage of the compounds of this invention isthat they have substantially less mammalian toxicity than comparablecompounds in the prior art.

These and other features, advantages and specific embodiments of thisinvention will become readily apparent to those exercising ordinaryskill in the art after reading the foregoing disclosures. Such specificembodiments are within the scope of the claimed subject matter unlessexpressly indicated to the contrary by claim language. Moreover, whilespecific embodiments of this invention have been described inconsiderable detail, variations and modifications of them can beeffected without departing from the spirit and scope of the invention asdisclosed and claimed. 1

The term consisting essentially of as used in this specificationexcludes any unrecited substance at a concentration sufficient tosubstantially adversely affect the essential properties andcharacteristics of the composition being defined, while permitting thepresence of one or more unrecited substances at concentrationsinsuflicient to substantially adversely affect said essential propertiesand characteristics.

What I claim and desire to protect by Letters Patent is:

1. An insecticidal composition, which comprises an insecticidallyeffective amount of insecticidal material represented by the formula:

wherein R is CH or C H R is alkyl having 1-19 carbon atoms, R and R areH or CH and Y is O or S.

3. A method according to claim 2 in which the insect is the southernarmyworm, and said material is applied to the seeds of a plant on whichsaid insect feeds.

References Cited UNITED STATES PATENTS 7/1958 Raley, Jr 260-309 3/ 1960McConnell et al. 260-3095 OTHER REFERENCES Judge, Chemical Abstracts,1970, vol. 72, No. 54031r.

ALBERT T. MEYERS, Primary Examiner D. R. ORE, Assistant Examiner UNITEDSTATES PATENT OFFICE (569) CERTIFICATE OF CORRECTION Patent No.3,816,621 Dated June 11 1974 Invgntor (a) Albe rt H Haube in ppesrs inthe above-identified patent It is certified that error e herebycorrected, as shown below:

and that said Letters Patent are rintedpatent, in the Tablepercent/percent 5 should read Column 3 of the p under column headed PA,

opposite Compound 5, 0/00 80/005 Signed and sealed this 1st day ofOetober 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

